text: Not every interaction between a photon and an atom, or molecule, will result in photoionization. The probability of photoionization is related to the photoionization cross section of the species – the probability of an ionization event conceptualized as a hypothetical cross-sectional area. This cross section depends on the energy of the photon (proportional to its wavenumber) and the species being considered i.e. it depends on the structure of the molecular species. In the case of molecules, the photoionization cross-section can be estimated by examination of Franck-Condon factors between a ground-state molecule and the target ion. This can be initialized by computing the vibrations of a molecule and associated cation (post ionization) using quantum chemical software e.g. QChem. For photon energies below the ionization threshold, the photoionization cross-section is near zero. But with the development of pulsed lasers it has become possible to create extremely intense, coherent light where multi-photon ionization may occur via sequences of excitations and relaxations. At even higher intensities (around  of infrared or visible light), non-perturbative phenomena such as barrier suppression ionization and rescattering ionization are observed.